Mixed Polycycloaliphatic Amines (MPCA) And MPCA Alkylates

ABSTRACT

Mixed polycycloaliphatic amines (MPCA) and alkylates thereof (MPCA alkylates), methods for making mixed polycycloaliphatic MPCA amines and MPCA alkylates thereof, as well as polymeric compositions, such as spray-applied polyurea coating compositions, comprising said mixed amines MPCA and MPCA alkylates thereof are described herein. In one embodiment, the polymeric composition comprises an isocyanate component, and a resin component comprising an organic compound having the following Formula I: 
     
       
         
         
             
             
         
       
     
     where R 1 , R 2  and R 3  are each independently selected from a hydrogen atom, an alkyl group comprising from 1 to 20 carbon atoms, an aryl group comprising from 3 to 12 carbon atoms, an aralkyl group comprising from 3 to 12 carbon atoms and combinations thereof, provided that there is at least one alkyl group within Formula I, and X is a methylene bridged polycycloaliphatic amine (MPCA).

BACKGROUND OF THE INVENTION

Disclosed herein are mixed polycycloaliphatic amines (MPCA) andalkylates thereof (MPCA alkylates), methods for making mixedpolycycloaliphatic MPCA amines and MPCA alkylates thereof, as well aspolymeric compositions, such as spray-applied polyurea coatingcompositions, comprising said mixed MPCA and MPCA alkylates.

The term “polymeric compositions”, as used herein, describescompositions comprising 2 or more repeating units. Specific examples ofpolymeric compositions include, but are not limited to, polyureas,polyurethanes, and urea/urethane hybrid elastomer or coatingcompositions. Certain polymeric compositions such as polyurea elastomersare rapid cure coatings that have gel times that can be as short as 2-3seconds. Because of its rapid cure speed, these polyurea coatings can beapplied over a broad range of temperatures, are relatively moistureinsensitive, and can be used on a wide variety of substrates. Inaddition to its application benefits, the fast cure speed may allowsusers and facility owners to return areas to service much faster thanwith other coatings systems, saving time and money for both thecontractors and owners. These benefits, among others, have all led tosignificant growth in the polyurea industry over the last two decades.

One problem in the industry has been a lack of standardization interminology; recent attempts to standardize the terminology include moreor less arbitrary definitions of “pure polyurea”, hybrid“polyurea-polyurethane” and “polyurethane” coatings. The impetus behindthe attempted standardization is the effect of cure speed and reactivityon both final properties of the cured system as well as the sensitivityof the system to moisture during the spray application process. Thesedelineations focus on the chemistry of the reaction process (as opposedto the chemistry in the manufacture of the components), where the curespeed and potential moisture sensitivity issues arise.

There are many examples of polyurea compositions in both the patent andscientific literature as well as many commercial systems that uses thesecoatings. Polyurea coatings can be formed by reacting an isocyanatecomponent with an isocyanate reactive component such as, for example aresin blend. The isocyanate component may be generally comprised of amonomer, polymer, or any variant reaction of isocyanates,quasi-prepolymer, prepolymer, or combinations thereof. The prepolymer orquasi-prepolymer can be made of an amine-terminated polymer resin, ahydroxyl-terminated polymer resin, or combinations thereof. Theisocyanate reactive component or resin blend may be generally comprisedof amine-terminated polymer resins, amine-terminated curing agents,hydroxyl-terminated polymer resins, hydroxyl-terminated curing agents,and combinations thereof. The term “curing agent” as used hereindescribes a compound or mixture of compounds that is added to apolymeric composition to promote or control the curing reaction. Incertain systems, the term “curing agent” may also describe chainextenders, curatives, or cross-linkers. The resin blend may also includeadditives or other components that may not necessarily react with theisocyanate contained therein as well as, in certain systems, catalysts.

While the compositions of these polyurea coatings vary, the isocyanatecomponent within the composition may be generally divided into two broadclasses: aromatic and aliphatic. The systems defined as aromatic may usean aromatic polyisocyanate, such as 4,4′-methylene bis isocyanto benzene(MDI), and isomers and adducts thereof. The MDI adducts referred to inboth the patent and scientific literature include MDI prepolymers,quasi-prepolymers (which have a mixture of prepolymer and high free MDImonomer level and may be prepared in-situ) and mixtures of MDIprepolymers and quasiprepolymers with other MDI monomer streams. MDIadducts are sometimes prepared using an MDI monomer with a high 2,4′-MDIisomer level to reduce the reactivity and increase the pot life. Forspray applied applications, the later property may be referred to as geltime and/or tack-free time. The composition may also employ one or moreadditional aromatic components such as, for example, the followingcuring agents, diethyl-toluenediamine (DETDA) ordithiomethyl-toluenediamine (ETHACURE® E300).

When the isocyanate component in the composition is aliphatic, thecuring agents that are used as the isocyanate reactive component aregenerally also aliphatic in nature. Examples of aliphatic curing agentsinclude, but are not limited to, dialkyl-methylene bis cyclohexylamine(which are marketed under the brandname CLEAR LINK®) or the asparticester products such as Desmophen® from Bayer Material Science LLC. Theremaining ingredients within the polymeric composition, which can beadded to either or both the isocyanate and resin blend components andcan be aromatic or aliphatic in nature, may include any number ofadditional components. Examples of additional ingredients in thepolymeric composition may include for, example, a polyalkylene oxide(i.e., polypropylene oxide) reacted into the polyisocyanate component toprovide a quasi-prepolymer and one or more amine-terminatedpolypropylene oxides of functionality 2.0 or higher, such as forexample, the JEFFAMINE® brand of curing agents.

Typical applications for polyurea compositions may include, for example,bedliners for pick-up trucks, pipe or pipeline coatings and linings,bridge coatings, joint fill and caulk, tank coatings and linings tocontain chemical and industrial liquids, marine coatings, roof coatings,waste water treatment linings, manhole and sewer linings, as well as anumber of additional applications falling under the general category of“protective coating” or liner. The polyurea composition may be appliedas sheets, fibers, foams, adhesives, coatings, elastomers, or othermethods. Depending upon its end-use and its application, it is desirablethat the polyurea composition exhibits at least one of the followingproperties: corrosion resistance, abrasion resistance, ease ofapplication, durability, fast cure time, adherence, high tensilestrength, high elongation, moisture insensitivity, flexibility, andcombinations thereof. Depending upon the end-use, it is also desirablethat the polymeric composition exhibit stability upon exposure to avariety of aggressive environments such as, for example, acids, bases,hydrocarbons, fuels, oxygenates, etc.

One of the more desired properties for polyurea compositions is improvedchemical resistance. For example, U.S. Publ. No. 2006/0058491 describesa polyurethane-polyurea polymer having a polyisocyanate component and anisocyanate-reactive component that includes at least one organiccompound having a mercaptan functional moiety such as a polysulfide.U.S. Pat. No. 6,797,789 describes phenolic/polyurea co-polymers thatcontain phenolic resins for improved chemical resistance performance.

There is a recognized need for a new family of curing agents whichprovide the end-user a tool to specifically tailor a wide-variety ofcure-profiles and which generally improve the overall formulatinglatitude of polymeric coating. Further, there may be a need in the artto provide a family of curing agents that may provide improved chemicalresistance.

BRIEF SUMMARY OF THE INVENTION

Mixed polycycloaliphatic amines (MPCA) and alkylates thereof (MPCAalkylates) which may be used as curing agents and polymeric compositionscomprising these mixed MPCA amines, MPCA alkylates, and combinationsthereof which may be used, for example, in plural component coatingapplications, are described herein. In one embodiment, there is providedpolymeric composition comprising: an isocyanate component, and a resincomponent that reacts with at least a portion of the isocyanatecomponent to provide the polymeric composition wherein the resincomponent comprises at least one polycycloaliphatic amine selected fromthe group consisting of 4,4′-methylenebis(cyclohexylamine),4-[(4-aminocyclohexyl)methyl]-cyclohexanol,2,4-bis[(4-aminocyclohexyl)methyl]-cyclohexylamine,4-[4-aminocyclohexyl)methyl-N-4-[4-[(4-aminocyclohexyl)methyl]-cyclohexyl]-cyclohexylamine,4-(p-aminobenzyl)cyclohexylamine, 2,4-bis(4′-aminocyclohexyl)aniline,and 2,4′-bis(4″-aminocyclohexyl)-2′,4-methylenedianiline, an alkylate ofthe at least one polycycloaliphatic amine, and mixtures thereof.

In another embodiment, there is provided a method for preparing apolymeric composition, the method comprising: providing an isocyanatecomponent; providing a resin component comprising a curing agentcomprising at least one polycycloaliphatic amine selected from the groupconsisting of 4,4′-methylenebis(cyclohexylamine),4-[(4-aminocyclohexyl)methyl]-cyclohexanol,2,4-bis[(4-aminocyclohexyl)methyl]-cyclohexylamine,4-[4-aminocyclohexyl)methyl-N-[4-[(4-aminocyclohexyl)methyl]cyclohexyl]-cyclohexylamine,4-(p-aminobenzyl)cyclohexylamine, 2,4-bis(4′-aminocyclohexyl)aniline,and 2,4′-bis(4″-aminocyclohexyl)-2′,4-methylenedianiline, an alkylate ofthe at least one polycyloaliphatic amine, and mixtures thereof; andmixing the at least a portion of the isocyanate component with at leasta portion of the resin component wherein the at least a portion of theresin component reacts with the at least a portion of the isocyanatecomponent to provide the polymeric composition wherein the volume ratioof the isocyanate component to the resin component in the polymericcomposition is any ratio in the range of from about 1.00:1.00 to about1.20:1.00.

In yet another embodiment, there is provided a polymeric compositioncomprising: an isocyanate component, and a resin component comprising anorganic compound having the following Formula I:

wherein R₁, R₂ and R₃ are each independently selected from a hydrogenatom, an alkyl group comprising from 1 to 20 carbon atoms, an aryl groupcomprising from 3 to 12 carbon atoms, an aralkyl group comprising from 3to 12 carbon atoms and combinations thereof, provided that there is atleast one alkyl group within Formula I, and X is a polycycloaliphaticamine.

In a further embodiment, there is provided a polymeric compositioncomprising: an isocyanate component, and a resin component comprising anorganic compound having the following Formula II:

where substituent R₄ is selected from a hydrogen atom, an alkyl groupcomprising from 1 to 20 carbon atoms, an aryl group comprising from 3 to12 carbon atoms, an aralkyl group comprising from 3 to 12 carbon atomsand combinations thereof, and X is a methylene bridgedpolycycloaliphatic amine.

In yet another embodiment, there is provided a polymeric compositioncomprising: an isocyanate component, and a resin component comprising anorganic compound having the following Formula III:

where substituent R₄ is selected from a hydrogen atom, an alkyl groupcomprising from 1 to 20 carbon atoms, an aryl group comprising from 3 to12 carbon atoms, an aralkyl group comprising from 3 to 12 carbon atomsand combinations thereof, and X is a methylene bridgedpolycycloaliphatic amine.

In a still further embodiment, there is provided a method for preparinga polymeric composition, the method comprising: providing an isocyanatecomponent; providing a resin component comprising an organic compoundhaving the following Formula I:

where R₁, R₂ and R₃ are each independently selected from a hydrogenatom, an alkyl group comprising from 1 to 20 carbon atoms, an aryl groupcomprising from 3 to 12 carbon atoms, an aralkyl group comprising from 3to 12 carbon atoms and combinations thereof, provided that there is atleast one alkyl group within Formula I, and X is a methylene bridgedpolycycloaliphatic amine; and mixing the at least a portion of theisocyanate component with at least a portion of the resin componentwherein the at least a portion of the resin component reacts with the atleast a portion of the isocyanate component to provide the polymericcomposition wherein the volume ratio of the isocyanate component to theresin component in the polymeric composition is any ratio in the rangeof from about 1.00:1.00 to about 1.20:1.00.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein are mixed polycycloaliphatic amines (MPCA) andalkylates thereof (MPCA alkylates) that may, for example, can providepolymeric compositions with improved chemical resistance, oralternatively, allow manufacturers and/or end-users to introduce changesto known formulations to improve the chemical resistance of an existingproduct. In the later embodiment, the mixed curing agents describedherein allows a manufacturer and/or end-user to improve existingformulations for specific applications with chemical resistance demandsranging from modest to aggressive, as measured by standard analyticaltechniques. Also described herein are polymeric compositions comprisingan isocyanate component and a resin component wherein at least a portionof the resin component is reactive to the isocyanate component andwherein the resin component comprises a mixed polycycloaliphatic amineand/or the alkylated derivatives of the mixed polycycloaliphatic aminesas a curing agent.

Polymeric compositions with increased cross-link density generallydemonstrate improved chemical resistance as measured by, for example,reduced swell, better retention of physical properties after exposure tochemicals (such as acidic environments, basic environments, certainsolvent environments, etc.), or both. While not intending to be bound bytheory, increased cross-link density can be affected by increasedhard-segment content, chemical cross-linking with amine-based curingagents with functionality greater than 2, or combinations thereof. It isbelieved that the chemical resistance of the polymeric composition maybe improved by the greater degree of cross-linking that results from theuse of these mixed aromatic and aliphatic curing agents such as thosedescribed herein.

In certain embodiments, the polymeric composition described hereincomprises 2 or more components: an isocyanate component and a resincomponent. The resin component may also be referred to herein as theisocyanate reactive component wherein at least a portion of theisocyanate reactive component reacts with at least a portion of theisocyanate component. In these embodiments, the polymeric compositions,such as polyurea and polyurethane polymers, comprise an isocyanatecomponent and a resin component, which are designated herein as anA-side and a B-side, respectively. The volume ratio of isocyanatecomponent and resin component present within the polymeric compositionmay be any ratio in the range of from about 10.00:1.00 to about1.00:10.00. Examples of such ratios include but are not limited to anyone of the following: about 10.00:1.00, 9.00:2.00, 8.00:3.00, 7.00:4.00,6.00:5.00, 5.00:5.00, 4.00:10.00, 3.00:9.00, 2.00:8.00, 1.00:10.00. Incertain preferred embodiments, such as those applications which relateto impingement mixing, the volume ratio of isocyanate component to resincomponent is any ratio in the range of from about 1.00:1.00 to about1.20:1.00 isocyanate to resin. For example, the volume ratio ofisocyanate component to resin component may be about 1.00:1.00, or about1.20:1.00, or about 1.00:1.20. Examples of suitable polymericcompositions containing isocyanate and resin components are thosedescribed in U.S. Pat. No. 6,403,752 which is incorporated herein byreference. The isocyanate component may comprise a polyisocyanate whichcan be a monomer, a quasi prepolymer, a full prepolymer, a blend ofpolyisocyanates, or combinations thereof. In embodiments wherein theisocyanate component comprises a full prepolymer, a full prepolymer maybe formed when the polyisocyanate is pre-reacted with a certain amountof polyamine or a polyol such that each reactive site of the polyamineor the polyol is covalently attached to one reactive site of apolyisocyanate. In these embodiments, the remaining unreacted sites ofthe polyisocyanate may be free to react further with the resin componentor B-side within the polymeric composition. In embodiments where theisocyanate component comprises a quasi prepolymer, a certain amount ofpolyamine or polyol may be present in the resin or B-side that is lessthan that necessary to form a full prepolymer is used. The result is amixture of prepolymer and a relatively higher amount of unreactedpolyisocyanate compared to a full prepolymer. In polymeric compositionswherein the isocyanate component comprises a polyisocyanate that ismonomeric or uses a quasi prepolymer, the isocyanate-reactive componentsin the resin component may comprise a blend of higher molecular weightcomponents (which add flexibility to the final polymer) and lowermolecular weight components (which tend to add to the strengthproperties of the final polymer). The term “higher molecular weight” isintended to indicate compounds having a molecular weight of greater than400; the term “lower molecular weight” is intended to indicate compoundshaving a molecular weight of 400 or less. In certain embodiments, theisocyanate component may be comprised of at least 2 isocyanate groups.In these or other embodiments, it could be comprised of a dimer ortrimer such as a hexamethylene diisocyanate (HDI) trimer.

As previously mentioned, the polymeric composition comprises anisocyanate component. The isocyanate component of the composition maycomprise an aliphatic isocyanate, an aromatic isocyanates, a prepolymer,a quasi-prepolymer derived from an isocyanate, and combinations thereof.The isocyanate may be comprised of aromatic isocyanates, aliphaticisocyanates, or combinations thereof. In embodiments where theisocyanate component contains one or more aromatic isocyanates, examplesof aromatic isocyanate compounds include, but are not limited to,methylene-bis-diphenylisocyanate (MDI) isomers, toluenediisocyanateisomers, phenylene diisocyanate isomers, sylylene diisocyanate isomersand Napthylene diisocyantes isomers. In one particular embodiment, thecomposition comprises a MDI isocyanate. In other embodiments, thecomposition comprises an aliphatic isocyanate in addition to, or in lieuof, the aromatic isocyanates. Examples of the aliphatic isocyanatesinclude, but are not limited to, hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (oneisomer mixture is marketed by Bayer under the trade name DESMODUR® W,for example). These isocyanate monomers may be modified and/or adductedto provide various desirable characteristics to the A-side of theformulation. It is understood that the isocyanate component is notintended to be limited to the above exemplary polyisocyanates and otherisocyanates may be used.

In one particular embodiment, the isocyanate monomer is modified bypreparing a prepolymer or quasi-prepolymer of the isocyanate with anisocyanate-reactive moiety with isocyanate-reactive functionality >=2.Polyols are commonly used and can include polypropylene glycol (PPGs),polytetramethylene glycols (PTMEGs), polyethylene glycols (PEGs),polyesters, polycaprolactones and blends and copolymers of these typesof isocyanate-reactive materials. As used herein, the term “polyol”refers to a single polyol or a blend of polyols. Diamines, thioethersand other isocyanate-reactive materials may also be used either alone orin combination.

The isocyanate component or A-side may also further contain variousother additives which may be reactive or non-reactive to the isocyanatecontained therein and/or the resin. The additional reactive componentsmay include components such as, but not limited to, reactive diluents(e.g., propylene carbonate), plasticizers, fillers, and pigments.Non-isocyanate-reactive species are used as pigments, fillers, adhesionpromoters and viscosity modifiers, for example. Other additives mayinclude, but are not limited to, stabilizers and plasticizers.

In certain embodiments, the amount of isocyanate component that is usedto produce the polymeric composition is dependent on the amount and theequivalent weight of the amine or curative portion of the formulation.In these embodiments, the range of equivalents of isocyanate groups toactive hydrogen atoms contained in the mixed polycycloaliphatic aminesdescribed herein may range from 0.75 to 1.25, or from 0.90 to 1.1, orfrom 0.95 to 1.05.

In certain embodiments, the functionality of the isocyanate componentmay range from 2 to about 3. Examples of such ranges include, but arenot limited to, any one of the following or combinations of thefollowing: 2 to 2.1; 2 to 2.3; 2 to 2.5; 2 to 2.8; 2.1 to about 3.0; 2.3to about 3.0; 2.5 to about 3.0; 2.8 to about 3.0; and combinationsthereof.

The polymeric compositions described herein may further compriseoligomeric polyisocyanates (e.g., dimers, trimers, polymeric, etc.) andmodified polyisocyanates (e.g., carbodiimides, uretone-imines, etc.) mayalso be used with the curing agents described herein in the resin side.In these embodiments, the polyisocyanates may be used “as-is” orpre-reacted.

As previously mentioned, the polymeric composition also comprises anisocyanate reactive component or a resin component or B-side component.The resin component may be composed of components where at least aportion of the resin reacts with at least a portion of the isocyanatecomponent contained therein and various other additives such as, but notlimited to, pigments, adhesion promoters, fillers, light stabilizers,catalyst, and combinations thereof. The isocyanate component(s) withinthe polymeric blend discussed herein are reacted or cured with a resinblend comprising the curing agent disclosed herein or the mixedpolycycloaliphatic amine and/or the alkylated derivatives of the mixedpolycycloaliphatic amines as a curing agent. Curing may occur eitherwith the diamine alone, or in combination with other polyamines orpolyols such as those described herein.

In one particular embodiment, the curing agent is an alkylated mixtureof methylene-bridged poly(cyclohexyl-aromatic) amines. Morespecifically, the polycycloaliphatic primary amines can be generallychemically characterized as poly(primary)aminocycloaliphatic substitutedcycloaliphatic amines, aromatic amines, methylene bridged cycloaliphaticamines, methylene bridged aromatic amines, or methylene bridged mixedcycloaliphatic/aromatic amines, where poly refers to at least twosubstituents and a maximum limited only by the possible open chemicalpositions. Examples of suitable aminoalkylcyclohexylamines include,4,4′-methylenebis(cyclohexylamine),4-[(4-aminocyclohexyl)methyl]-cyclohexanol,2,4-bis[(4-aminocyclohexyl)methyl]-cyclohexylamine,4-[4-aminocyclohexyl)methyl-N-[4-[(4-aminocyclohexyl)methyl]cyclohexyl]-cyclohexylamine,and the like. Commercial mixtures of aminoalkylcyclohexylamines andaminoaralkylcyclohexylamines are sold under the trade name “MixedPolycycloaliphatic Amines” (MPCA) by the assignee of the presentapplication. In one embodiment, the methylene-bridgedpoly(cyclohyexyl-aromatic amines) are the residue obtained from thedistillation of a mixture of poly(cyclohexyl aromatic) amines formed bythe hydrogenation of crude methylene dianiline or cureddi(4-amino-3-methylcyclohexyl)methane. Further examples of suitablemixed polycycloaliphatic amines that are used as a curing agent in apolymeric composition are described, for example, U.S. Pat. No.5,280,091. Useful alkylates of these mixed polycycloaliphatic amines(MPCA) include organic compounds having the following general Formula I:

where R₁, R₂ and R₃ are each independently selected from a hydrogenatom, an alkyl group comprising from 1 to 20 carbon atoms, an aryl groupcomprising from 3 to 12 carbon atoms, an aralkyl group comprising from 3to 12 carbon atoms and combinations thereof, provided that there is atleast one alkyl group within Formula I, and X is a methylene bridgedpoly(cycloaliphatic-aromatic) amine (MPCA). If R₁, R₂ and/or R₃ arealkyl groups, the alkyl groups are either linear or branched alkylgroups comprising from 1 to 20, or from 2 to 12, or from 2 to 6 carbonatoms. Representative alkyl groups include methyl, ethyl, propyl,isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, and thevarious isomeric pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.Any one or all of alkyl group, aralkyl group, and/or aryl group may besaturated or unsaturated. As previously mentioned, the structure inFormula I is attached to X which is a polycycloaliphatic amine such asMPCA. In the Formula I, substituents R₁, R₂ and R₃ are attached to X orMPAC at a nitrogen atom that that initially had one or two hydrogenatoms attached. In certain embodiments, the curing agent is one or morenon-alkylated MPCAs. In other embodiments, the curing agent is one ormore alkylated MPCAs. In still further embodiments, the curing agent isa mixture of one or more non-alkylated MPCA and one or more alkylatedMPCA.

In certain embodiments, the alkyl group, the aryl group, or the aralkylgroup may be substituted with one or more hetero atoms such as, but notlimited to, O, N, and S. In these or other embodiments, the alkyl group,the aryl group, or the aralkyl group may be substituted with one or morearomatic groups. In these embodiments, it may be preferably that thesubstituents within the organic compound having the above Formula I arenot detrimental to the reaction that provides the polymeric compositionsuch as, but not limited to, reductive alkylation. For example, ethersmay be present within the compound provided that they do not react;however, thioethers may interfere with the catalyst required to performthe reductive alkylation. The substituent groups that may be presentwithin the organic compound without interfering with the catalyst willbe known to those skilled in the art.

In one particular embodiment, the mixed polycycloaliphatic amines areprepared using a reductive alkylation method. The reductive alkylationpreparation method may use, for example, aldehydes or ketones to providethe hydrocarbon fragments in the reaction product. The identity of thealdehyde or ketone will determine the identities of each R substituentor R₁, R₂ and R₃ provided in Formula I and in the resulting reactionproduct. The structures below, or A, B, and C, are various embodimentsof the mixed polycyloaliphatic amines described herein and not intendedto be limited thereto. These embodiments illustrate the hydrocarbonfragment which may be formed by using acetone, methyl isobutyl ketoneand benzadehyde in the preparation of the MPAC reaction product orstructures A, B and C, respectively.

In one embodiment, any one of the R substituents or R₁, R₂, or R₃ in thereaction product may independently contain oxygen moieties in the formof ethers.

In another embodiment, the alkylate group may also be composed offragments from the reaction with an epoxy group, such as, for example,ethylene oxide (EO) or propylene oxide (PO) as a component of thealkylation process to form a reaction product having the followingFormula II:

In the above Formula II, substituent R₄ is selected from a hydrogenatom, an alkyl group comprising from 1 to 20 carbon atoms, an aryl groupcomprising from 3 to 12 carbon atoms, an aralkyl group comprising from 3to 12 carbon atoms and combinations thereof, and X is a methylenebridged polycycloaliphatic amine (MPCA). In one embodiment, R₄ may be,for example H, if an ethylene oxide is used in the alkylation process.In another embodiment, R₄ may be, for example, CH₃ if a propylene oxideis used in the alkylation process.

In a further embodiment, R₄ may be, for example, a short oligomer thatis formed from, for example, ethylene oxide (EO) or propylene oxide (PO)in the alkylation process to provide a reaction product having thefollowing Formula III. In these embodiments, the reaction of the aminewith the EO or PO does not necessarily require a reductive alkylationreaction. The resultant reaction product or compound having Formula IIIare isocyanate reactive but are significantly slower than theamine-isocyanate reaction. In Formula III, substituent R₄ is selectedfrom a hydrogen atom, an alkyl group comprising from 1 to 20 carbonatoms, an aryl group comprising from 3 to 12 carbon atoms, an aralkylgroup comprising from 3 to 12 carbon atoms and combinations thereof, Xis a methylene bridged polycycloaliphatic amine (MPCA), and n is anumber ranging from 1 to 10:

In the above Formula III, the length of the oligomer is not limitedthereto. In certain embodiments, the desired reaction product will havean average of no more than about one unit attached to each nitrogen atomcontained within the reaction product. In this or other embodiments, ndenotes a number ranging from 1 to 3 which may be attributable to therelatively higher reaction rate with N than with O. In this particularembodiment, the hydroxyls do not participate in the polyurea reaction,since their reaction rate will be much lower than the amines, retaininga designation of pure polyurea. The term “pure polyurea” as used hereinis a polyurea elastomer whose starting components are isocyanatefunctional on one side and amine functional on the other. The aminefunctional side of the elastomer is further defined as having onlyminimal intentionally added hydroxyl functionality that is reactive withthe isocyanate. The “minimal” amount may range from about 0 to about 20%added hydroxyl.

In one particular embodiment, the MPCA mixed alkylates comprises amixture of amines reflecting the composition of the distillate residue.In this embodiment, the major components of the residue are thefollowing which also includes the weight percent range based upon theoverall mixture of curing agent:

Ingredient: CAS No. Range (%) 1. Di(4-aminocyclohexyl)methane (“PACM”)1761-71-3 0-10%

2. 4-[(4-aminocyclohexyl)methyl]cyclohexanol (“PACM—OH”) 52314-58-60-25%

3. (“1/2-PACM”) 26480-77-5 0-30%

4. (“Three Ring”) 25131-42-4 0-50%

5. (“Three Ring”) N.A. 0-40%

6.4-[(4-aminocyclohexyl)methyl]-N-[4-[(4-aminocyclohexyl)methyl]cyclohexyl]69868-18-4 0-35%

In certain embodiments, the MPCA alkylates comprises at least one of orall of the above major ingredients, 1, 2, 3, 4, 5, 6, and combinationsthereof.

The MPCA alkylates replace up to an average of one hydrogen per nitrogenwith the alkylate fragments discussed. Replacement of more than anaverage of one hydrogen atom per nitrogen atom may result in anunacceptable level of chain terminating molecules with respect toreaction with isocyanate and may also result in poor performance of theresultant polymer in terms of physical properties and/or chemicalresistance. Generally, a replacement of greater than 20% may result inan unacceptable loss in properties and/or performance.

The isocyanate-reactive components comprising the B-side of the spraypolyurea system include predominantly amine-functional chain extendersand crosslinkers, but may also include a portion of polyols or otherisocyanate-reactive chain extenders and crosslinkers. The distinctionbeing the terms “chain extender” and “cross linker” is functionality ofthe isocyanate reactive moiety, e.g., chain extenders have afunctionality of 2 whereas cross linkers have functionality >2. Commonlyused amines include, but are not limited to, diethyl-toluenediamine(DETDA, also known as E100 from Albermarle), dimethylthiotoluenediamine(also known as E300 from Albermarle), alkyl methylenedianiline (alkylMDA from Unilink products), and any one of a series ofdiaminopoly(propylene glycols) are also commonly used such as D230, D400and D2000, where the numeric designator refers to the overall molecularweight. Higher functionality products with similar backbones are alsocommonly used, such as, for example, JEFFAMINE T5000, a 5000 molecularweight trifunctional poly(propylene glycol) triamine. Many otheraromatic and aliphatic amines can also be used as components. Polyolcomponents of functionality of at least 2 can be employed, such aspoly(propylene glycol), ethylene oxide-capped polypropylene glycol,other polyethers, polyesters and polycaprolactones. In polyureaformulations the polyols are employed at a lower level than the totalamine, usually at 20% or less of the B-side to maintain ability todesignate the system as a pure polyurea. Polyurethane-polyurea hybridsemploy polyols in the B-side of the spray formulation of >20%, and purepolyurethanes employ all polyols in the B-side of the system. The B-sidemay also contain a number of other components including plasticizers(isocyanate-reactive or non-reactive), fillers, pigments, and/orcatalysts for example.

The A-side and B-sides can be formulated depending upon the needs of thefinal product. In certain embodiments, the A and B sides are blended ina plural-component spray equipment. Due to the fast nature of thepolyurea cure, plural-component spray equipment may be used to mix,spray and apply the A and B sides of the polymeric composition onto asubstrate to provide a coating or a coated substrate. In theseembodiments, the polymeric composition is produced and applied toprovide a coating onto a substrate using plural component sprayequipment includes two or more independent chambers for holding aisocyanate component and an resin component. Flowlines connect thechambers to a proportioner which appropriately meters the two components(A-side and B-side) to heated flowlines, which can be heated by a heaterto the desired temperature and pressurized. In certain embodiments, thespray operation can be conducted at a pressure ranging from about 1,000psi and about 3,500 psi. In this or other embodiments, the sprayoperation can be conducted at temperatures ranging from about 120° toabout 190° F. In still further embodiments, the temperature may be aslow as room temperature. Once heated and pressurized, the two or morecomponents are then fed to a mixing chamber located in the spray-gunwhere they are impingement mixed before being sprayed through the nozzleand onto the substrate. Most coating systems which use plural componentspray equipment for application have very quick cure times and begin tocure as a polymer layer on the substrate within seconds. Suitableequipment may include GUSMER® H-2000, GUSMER® H-3500, and GUSMER®H-20/35 type proportioning units fitted with an impingement-mix sprayguy such as the Grace FUSION, GUSMER® GX-7 or the GUSMER® GX-8 (allequipment available from Graco-Gusmer of Lakewood, N.J.). Functionallysimilar equipment is available from a wide range of manufacturers.

In one particular embodiment, the polymeric composition is made andapplied using a GUSMER® H20/35 which is designed for a 1:1 volume mixand spray ratio. In the case of a 1:1 ratio, the A-side and B side areformulated such that upon mixing the curative will be present at 95% ofthe theoretical stoichiometry, however, this ratio can be altered withina +/−10% to achieve specific, desired results in the final polyurea.Commonly available A-side polyurea spray components are often in the14-16% NCO range. However, the formulation of the A-side or isocyanatecomponent is not limited to this particular % NCO range. The formulationlatitude of the A and B side of the spray polyurea formulation islimited only by the available materials and the availability of suitablespray equipment to accommodate the resultant ratio (i.e., 1:10 to 10:1for example).

Although plural-component spray equipment is described herein as amethod of applying the light-stable polymeric compositions describedherein, other methods may be used in preparing and forming the polymericcompositions. For example, the polymeric composition may be formed usingcompression molding or injection molding processes, such as reactioninjection molding (RIM) processes. Furthermore, if formulated into aslow-cure system, the polymeric composition can be applied via othertechniques, such as but not limited to, roll-on, low-pressure spray,dip, or trowel techniques.

Illustrative, but non-limiting, examples are set forth below. In thefollowing examples unless otherwise specified, area percent gaschromatography (GC) analysis was conducted using a 25 m long with a 0.17micron film thickness HP-5 column. The test results in Tables III and IVfor the physical properties of the polymeric coatings were obtainedusing the ASTM D-412 standard using a Die C test coupon at a pull a rateof 2 inches/minute. The tear strength was obtained using the ASTM D-624standard.

EXAMPLES Example 1A Preparation of MPCA-Acetone Reductive Alkylate

Starting material of the mixed polycylcoaliphatic (MPCA) amines wasanalyzed using GC analysis and found to contain the following which isprovided in weight percent:

PACM (Ingredient 1) 5.4% PaCM-OH (Ingredient 2) 4.9% ½ PACM (Ingredient3) 11.0% 3 ring (Ingredients 4 and 5) 56.5% Secondary amines (Ingredient6) 21.7%The above mixture further included a catalyst or 10% palladium on carbon(50% wet) which brought the total weight percent of the mixture to 100%.

A 2198 gram (g) or 6.97 molar amount of the above MPCA mixture wascombined with 1424 grams (24.55 moles) acetone, and rolled in a 2 gallonNalgene container until the mixture was homogeneous to provide apre-mixture of MPCA and acetone. A 6.0 g amount of palladium on carbon(Pd/C) catalyst was charged to a 1.5 gallon reactor followed byapproximately 3572 grams of the pre-mixture of MPCA and acetone. Thereactor was purged several times with nitrogen (N₂) and determined to bepressure-tight and then purged and leak-checked with hydrogen (H₂) at apressure of 435 pounds per square inch (psi). The stir rate was set at100 revolutions per minute (rpm) and the temperature was ramped to atemperature of 80° C. at which point the reactor was set at a constant800 psi H₂ pressure. The reaction was allowed to proceed forapproximately 21 hours while monitoring the H₂ ballast pressure. Therate of H₂ ballast pressure decrease indicated the reaction wassubstantially complete in approximately 8.4 hours. The crude reactionmixture was filtered to remove any catalyst not consumed in the reactionand then vacuum evaporated to provide the isopropyl MPCA. A Karl-Fischerwater analysis indicated that there was 350 parts per million (ppm)water in the product. Amine titration results showed 6.77 meq/g (147.7g/eqv) versus non-alkylated MPCA 112 g/eqv, indicating successfulalkylation had occurred. The increase in equivalent weight of 36indicates an alkylation level of approximately (36/42) 0.86 units pernitrogen.

Example 1B Preparation of an MPCA-Acetone Reductive Alkylate

A 1 liter, stainless steel (SS) vessel was charged with 300 grams (0.95m MPCA) from the Example 1A, 6.0 g 2% Pd/C catalyst, and 30 gramsisopropyl alcohol. The mixture was heated to a temperature ofapproximately 60 to 70° C. and a pressure of 100 psi H₂ and then 190.8grams (3.3 moles) acetone was added over a period of 10 minutes. Themixture was then heated to a maximum temperature of 130° C. and amaximum pressure of 800 psi H₂. Monitoring of the H₂ pressure showedsignificant uptake of H₂. This procedure was repeated using 260 g (0.82moles) MPCA, 70 g isopropyl alcohol, and 165.4 g (2.85 moles) acetone.An additional ½ charge (3.0 g) of the 2% Pd/C catalyst was added. Thetwo runs were combined and filtered in THF through a 0.2 μm filter atapproximately 50° C. Gas Chromatographic analysis indicated the two runseach produced a complex mixture of products but resulted in the initialmix of eluents nearly disappearing and a new band of later elutingcomponents appearing as is characteristic of an alkylated species. Afterstripping the solvent, the AEW was determined by titration to be 149 andthe specific gravity to be 0.97. The AEW indicates an alkylation levelof approximately (37/42) 0.88 per nitrogen.

Example 1C Preparation of MPCA-MIBK Reductive Alkylate

An amount of 20.5 grams 10% Pd/C catalyst (50% wet) (3 wt % based onMPCA+MIBK) was charged to a one liter SS reactor, followed by 149.8grams (0.48 m) MPCA dissolved in 165.75 grams (1.66 m) methyl isobutylketone (MIBK). The reactor was purged three times and leak checked withN₂, then purged three times and leak checked with H₂. The reaction mixwas heated to 90° C. and charged with 100 psi H₂ connected to a H₂ballast tank. The reaction was allowed to proceed 22 hours then the H₂pressure raised to 800 psi and allowed to proceed an additional 5 hours.The crude reaction mixture was then filtered through 0.5 μm filter usinga pressure filter apparatus, followed by removal of excess MIBK byvacuum evaporation. The GC analysis shown below in Table I indicatedalkylation had occurred, and the amine titration showed 5.58 meg/g (AEW179.2 g/eqv). The AEW indicates an alkylation level of (67/86) 0.78 pernitrogen.

TABLE I GC Area % analysis Retention time MPCA MIBK-alkylate <26 minutes30.71 0 26-35 minutes 0 89.01 35-40 minutes 68.29 10.99 1) Data forpeaks eluting at or before 40 minutes only.

Example 2 Preparation of a Polyurea Polymer Containing the MPCA—MethylIsobutyl Ketone (MIBK) Reductive Alkylate

A polyurea B-side or resin component was prepared which was comprised of28% MPCA-methyl isobutyl ketone (MIBK) reductive alkylate which wasprepared in a manner similar to Example 1C above, 8.4% E100 (provided byAldermarle Corp.), 2% JEFFAMINE® T-5000, 31.5% JEFFAMINE® D2000 and 30%JEFFAMINE® SD-2001 (which is a Jeffamine D2000 alkylate). The A-side orisocyanate component was comprised of Rubinate 9480 (provided byHuntsman Corp.). Both A and B components were heated to approximately160° F. and sprayed onto a waxed metal panel at a pressure ofapproximately 2500 psi, using a GUSMER® GX-7 impingement mix spray gun.Two sheets of approximate size 18″×18″ were prepared, with one sheetbeing cured overnight (approximately 16 hours) at 70° C. and the secondsheet being allowed to cure under ambient conditions for at least 30days before testing. The plaque was observed to have a gel time of 4seconds and a tack-free time of 7 seconds.

Example 3 Preparation of a Polyurea Polymer Containing the MPCA-AcetoneReductive Alkylate

A polyurea B-side or resin component was prepared which was comprised of25% MPCA-acetone reductive alkylate, 5.6% E100 (provided by AldermarleCorp.), 2% JEFFAMINE® T-5000, 38% JEFFAMINE® D2000 and 30% JEFFAMINE®SD-2001 (a Jeffamine D2000 alkylate). The A-side or isocyanate componentwas comprised of Rubinate 9480 (Huntsman Corp.). Both A and B componentswere heated to approximately 160° F. and sprayed onto a waxed metalpanel at a pressure of approximately 2500 psi, using a GUSMER® GX-7impingement mix spray gun. Two sheets of approximate size 18″×18″ wereprepared, with one sheet being cured overnight (approximately 16 hours)at 70° C. and the second sheet being allowed to cure under ambientconditions for at least 30 days before testing. The plaque was observedto have a gel time of 4 seconds and a tack-free time of 7 seconds.

Example 4 Preparation of a Polyurea Polymer Containing an MPCA-AcetoneReductive Alkylate

A polyurea B-side or resin component was prepared which was comprised of27% MPCA-acetone reductive alkylate, 9% E300 (provided by AldermarleCorp.), 3% JEFFAMINE® T-5000, 36% JEFFAMINE® D2000 and 25% JEFFAMINE®SD-2001 (a Jeffamine D2000 alkylate). The A-side or isocyanate componentwas comprised of Rubinate 9480 (Huntsman Corp.). Both A and B componentswere heated to approximately 160° F. and sprayed onto a waxed metalpanel at a pressure of approximately 2500 psi, using a GUSMER® GX-7impingement mix spray gun. A sheet of approximate size 18″×18″ wereprepared, with one sheet being cured overnight (approximately 16 hours)at 70° C. before testing. The plaque was observed to have a gel time of18 seconds and a tack-free time of 29 seconds. Other measurements of thetest coupon where obtained and are as follows: Hardness=94 Shore A usingASTM D-2240; Tensile strength=1936 psi; % Elongation=143; and 100%Modulus=1616 psi using ASTM D-412; Die C tear=352 pli using ASTM D-624;and Split tear=44 pli using ASTM D-470.

Example 5 Preparation of a Polyurea Polymer Containing MPCA(Non-Alkylated)

A polyurea part B amine resin blend component was prepared consisting ofa mixture of 7% MPCA, 5.6% E100, 2% Jeffamine T-5000, 38% JeffamineD2000 and 30% Jeffamine SD-2001 (a Jeffamine D2000 alkylate). The A-sideor isocyanate component was comprised of Rubinate 9480 (Huntsman Corp.).Both A and B components were heated to approximately 160 F and sprayedonto a waxed metal panel at a pressure of approximately 2500 psi, usinga GUSMER® GX-7 impingement mix spray gun. Two sheets of approximate size18″×18″ were prepared (6 sec gel time, 12 sec tack-free time), with onesheet being cured overnight (approximately 16 hours) at 70° C. and thesecond sheet being allowed to cure under ambient conditions for severalweeks before testing.

Example 6 Preparation of a Polyurea Polymer Containing MPCA(Non-Alkylated)

A polyurea part B amine resin blend component was prepared consisting ofa mixture of 5% MPCA, 23.9% E100, 71.1% Jeffamine D2000. The A-side orisocyanate component was comprised of Polyshield part A (provided by SPIcorp.). Both A and B components were heated to approximately 160° F. andsprayed onto a waxed metal panel at a pressure of approximately 2500psi, using a GUSMER® GX-7 impingement mix spray gun. One sheet ofapproximate size 18″×18″ was prepared and cured approximately one weekat ambient conditions then 16 hours at 70° C. before testing. The plaquewas observed to have a gel time of 2 seconds and a tack-free time of 4seconds.

Example 7 Preparation of a Polyurea Polymer Containing Alkylated MPCA(Acetone Reductive-Alkylate)

A polyurea part B amine resin blend component was prepared consisting ofa mixture of 15% MPCA-acetone reductive alkylate, 19% E100, 66%Jeffamine D2000. Polyshield part A (SPI corp.) was used as the A (orisocyanate-containing) component. Both A and B components were heated toapproximately 160° F. and sprayed onto a waxed metal panel at a pressureof approximately 2500 psi, using a GUSMER® GX-7 impingement mix spraygun. One sheet of approximate size 18″×18″ was prepared and curedapproximately one week at ambient conditions then 16 hours at 70° C.before testing. The plaque was observed to have a gel time of 2 secondsand a tack-free time of 4 seconds.

Comparative Example A

A polyurea plaque of a commercially available material, Polyshield HT,which was obtained from Specialty Products, Inc. of Lakewood, Wash.(“SPI HT”), was prepared in a fashion similar to Example 2 forcomparison.

Comparative Example B

A polyurea plaque of a commercially available material, EnviroLasticAR425, which was obtained from the General Polymers division of TheSherwin-Williams Company of Cincinnati, Ohio, was prepared in a fashionsimilar to Example 2 for comparison.

Comparative Example C

A polyurea plaque of a commercially available material, PolyshieldSS-100, which was obtained from Specialty Products, Inc. of Lakewood,Wash. was prepared in a fashion similar to Example 2 for comparison. Thegel time was 4 seconds and the tack-free time was 8 seconds.

Comparative Examples D, E, F, and G

Comparative Examples D, E, F, and G were prepared according to thereference article Reddinger, Jerry L.; Hillman, Kenneth M., “Tuning theProperties of Polyurea Elastomer Systems using Raw Material Selectionand Processing Parameter Modulation”, PU Latin America 2001,International Polyurethanes Conference & Exhibition for Latin America,Conference Papers, Sao Paulo, Brazil, Aug. 28-30, 2001 (2001),P32/1-P32/7. CODEN: 69COBM CAN 137:264227 AN 2002:357450 CAPLUS.

The A-side of the formulation of comparative examples D through G wasMDI-based with a % NCO of 15.4%, such as Rubinate® 9480, a quasiprepolymer described as having high 2,4-MDI content. Example G was a MDIquasi prepolymer with a % NCO of 19.6%.

The B-side of the formulation of the comparative examples is set outbelow in Table II. In each case, the polyurea elastomer was preparedusing a 1:1 volume ratio of the A-side to the B-side with a weight ratioof approximately 1.1 to 1.15/1.

TABLE II B-Side Component of Comparative Examples D through GJeffamine ® Jeffamine ® Jeffamine ® Unilink ® Comp. Ex. D2000 T5000 D4004200 DETDA Iso Index D 65.68 5.57 28.76 1.05 E 57.45 10.64 10.64 21.281.10 F 33.54 10 20 15 21.5 1.10 G 52.02 5.33 29.85 12.79 1.05

Comparison of the Polymeric Compositions

Chemical swell data in Table V was obtained in the following manner.Coupons of dimension 1″×3″ were cut from sprayed plaques of ˜ 1/16″ inthickness. The individual coupons were weighed (dry) and fully immersedin the indicated liquid in Table V. After the time period specified, thecoupons were removed from the liquid, blotted dry and weighed. Thedifference in the weight after immersion minus the starting weightdivided by the starting weight is the reported percentage weight change.

The three commercial spray polyurea formulations, Envirolastic AR425from Sherwin-Williams Co., Polyshield SS-100 and Polyshield HT both fromSPI, were obtained from the manufacturers in two part formulations andsprayed following manufacturers recommendations. The plaques were curedovernight at 70° C. before testing, unless otherwise indicated.

The data in the Tables III through V show that the MPCA alkylates can beeasily formulated to provide physical properties similar to those of awide selection of formulated polyurea systems. In addition, the chemicalswell data show both MPCA alkylates to have better chemical swellresistance to jet fuel than all of the commercial polyurea formulationsevaluated. Both alkylates also showed much better resistance to H₂SO₄than the commercial formulations. Additional improvements were alsonoted, for example the MPCA-MIBK formulation showed outstandingresistance to HCl, much better than two of the commercial formulationsand similar to the third. The comparison of the MPCA-MIBK formulation tothe AR425 polymeric formulation (which has similar HCl resistance) showsthe MPCA-MIBK formulation to have better resistance to all of theremaining chemicals tested which shows the unique ability to matchspecific chemical resistance targets while improving upon broad spectrumchemical resistance. The non-alkylated MPCA was also shown to be able tobe formulated into a spray polyurea system. However, for certainembodiments, the higher reaction rate may limit the amount ofnon-alkylated MPCA that can be used in the total polyurea formulation.

TABLE III Comparison of Physical Properties of Polymeric CompositionsDescribed Herein Description Ultimate Elongation Die C of Curing Shore ATensile @ break 100% 200% 300% tear Split Ex. Agent hardness (psi) (%)modulus modulus modulus (lbf/in) Tear 5 MPCA non- 93 2315 358 1045 13751894 420 91 alkylated 7 MPCA 2560 182 1597 501 alkylated 3 MPCA- 93 2433197 1669 — — 514 74 acetone (FC)¹ 3 MPCA- 94 2393 194 1819 — — 502 54acetone (ambient)² 2 MPCA- 93 2549 260 1610 2051 — 538 78 MIBK (FC)¹ 2MPCA- 95 2670 234 1845 2379 — 532 70 MIBK (ambient)² 6 MPCA non- 2426145 1808 474 alkylated 4 MPCA 94 1936 143 1616 352 44 Acetone alkylate(FC)¹: Sheet was cured overnight (approximately 16 hours) at 70° C.(ambient)²: Sheet was cured under ambient conditions for at least 30days before testing

TABLE IV Comparison of Physical Properties of Comparative Prior ArtCompositions Ultimate Elongation Die C Comp. Tensile @ break 100% 200%300% tear Split Gel Tack-free Ex. (psi) (%) modulus modulus modulus(lbf/in) Tear time time D 2488 467 1212 — 1823 505 — 4 7 E 2662 532 1173— 1753 482 — 5.5 10 F 2772 268 1946 — — 541 — 3.5 6.5 G 2128 529 10271471 456 7 12.5 A 3757 513 1112 1458 1932 565 — B 2090 403 1063 13231688 421 89 C 2860 226 1397 467

TABLE V Chemical Swell Data (Measured in Percent Weight Gain after 24hour, 72 hour, and 7 day exposure) Ex. Gas Jet Xylene Methanol H₂SO₄ HCL3 37 (24 hr) 4.8 (24 hr) 90 (24 hr) 80 (24 hr) 18 (24 hr) 3 (24 hr) 43(72 hr) 9 (72 hr) 109 (72 hr) 91 (72 hr) 35 (72 hr) 6 (72 hr) 46 (7 day)13 (7 day) 118 (7 day) 97 (7 day) 57 (7 day) 16 (7 day) 2 36 (24 hr) 5(24 hr) 92 (24 hr) 70 (24 hr) 20 (24 hr) 0.7 (24 hr) 41 (72 hr) 10 (72hr) 102 (72 hr) 75 (72 hr) 41 (72 hr) 1.2 (72 hr) 43 (7 day) 14 (7 day)108 (7 day) 78 (7 day) 68 (7 day) 2.6 (7 day) 6 21 (24 hr) 2.8 (24 hr)60 (24 hr) 47 (24 hr) 19.5 (24 hr) 9.5 (24 hr) 27 (72 hr) 5.3 (72 hr) 49(72 hr) 39 (72 hr) 40 (72 hr) 22 (72 hr) 22 (7 day) 8.8 (7 day) 43 (7day) 25 (7 day) 64 (7 day) 31 (7 day) 7 20.5 (24 hr) 3.4 (24 hr) 57 (24hr) 41 (24 hr) 18.4 (24 hr) 9.1 (24 hr) 27 (72 hr) 6.3 (24 hr) 44 (72hr) 32 (72 hr) 37 (72 hr) 21 (72 hr) 20 (7 day) 9.4 (24 hr) 38 (7 day)22 (7 day) 56 (7 day) 29 (7 day) Comp. 59 (24 hr) 12 (24 hr) 135 (24 hr)90 (24 hr) 28 (24 hr) 1.4 (24 hr) Ex. B 67 (72 hr) 19 (24 hr) 146 (72hr) 94 (72 hr) 54 (72 hr) 1.7 (72 hr) 71 (7 day) 22 (24 hr) 152 (7 day)95 (7 day) 84 (7 day) 2.3 (7 day) Comp. 41 (24 hr) 13 (24 hr) 88 (24 hr)70 (24 hr) 49 (24 hr) 6 (24 hr) Ex. A 44 (72 hr) 17 (72 hr) 95 (72 hr)71 (72 hr) 92 (72 hr) 10 (72 hr) 45 (7 day) 19 (7 day) 99 (7 day) 71 (7day) 98 (7 day) 16 (7 day) Comp. 21.3 (24 hr) 4.7 (24 hr) 56 (24 hr) 42(24 hr) 26 (24 hr) 14 (24 hr) Ex. C 28 (72 hr) 8.5 (72 hr) 41 (72 hr) 34(72 hr) 54 (72 hr) 28 (72 hr) 21 (7 day) 11 (7 day) 34 (7 day) 23 (7day) 82 (7 day) 34 (7 day)

1-8. (canceled)
 9. A polymeric composition comprising: an isocyanatecomponent, and a resin component comprising an organic compound havingthe following Formula I:

wherein R₁, R₂ and R₃ are each independently selected from a hydrogenatom, an alkyl group comprising from 1 to 20 carbon atoms, an aryl groupcomprising from 3 to 12 carbon atoms, an aralkyl group comprising from 3to 12 carbon atoms and combinations thereof, provided that there is atleast one alkyl group within Formula I, and X is a methylene bridgedpolycycloaliphatic amine.
 10. A polymeric composition comprising: anisocyanate component, and a resin component comprising an organiccompound having the following Formula II:

where substituent R₄ is selected from a hydrogen atom, an alkyl groupcomprising from 1 to 20 carbon atoms, an aryl group comprising from 3 to12 carbon atoms, an aralkyl group comprising from 3 to 12 carbon atomsand combinations thereof, and X is a methylene bridgedpolycycloaliphatic amine.
 11. A polymeric composition comprising: anisocyanate component, and a resin component comprising an organiccompound having the following Formula III:

where substituent R₄ is selected from a hydrogen atom, an alkyl groupcomprising from 1 to 20 carbon atoms, an aryl group comprising from 3 to12 carbon atoms, an aralkyl group comprising from 3 to 12 carbon atomsand combinations thereof, and X is a methylene bridgedpolycycloaliphatic amine.
 12. A method for preparing a polymericcomposition, the method comprising: providing an isocyanate component;providing a resin component comprising an organic compound having thefollowing Formula I:

where R₁, R₂ and R₃ are each independently selected from a hydrogenatom, an alkyl group comprising from 1 to 20 carbon atoms, an aryl groupcomprising from 3 to 12 carbon atoms, an aralkyl group comprising from 3to 12 carbon atoms and combinations thereof, provided that there is atleast one alkyl group within Formula I, and X is a methylene bridgedpolycycloaliphatic amine; and mixing the at least a portion of theisocyanate component with at least a portion of the resin componentwherein the at least a portion of the resin component reacts with the atleast a portion of the isocyanate component to provide the polymericcomposition wherein the volume ratio of the isocyanate component to theresin component in the polymeric composition is any ratio in the rangeof from about 1.00:1.00 to about 1.20:1.00.